The present invention relates to detergent compositions or components comprising a specific hydrophobically modified cellulosic polymer and one or more quatemary ammonium compounds.
It is known that fabrics and textiles simply wear out over time and with use. Also, the laundering of the fabrics and textiles, over many cycles, can accentuate and contribute to the deterioration of the integrity and the appearance of such fabrics and textiles. Deterioration of fabric integrity and appearance can manifest itself in several ways. For example, short fibers are dislodged from woven and knit fabric/textile structures by the at mechanical action of laundering. These dislodged fibers may form lint, fuzz or xe2x80x9cpillsxe2x80x9d which are visible on the surface of fabrics and diminish the appearance of newness of the fabric. Further, repeated laundering of fabrics and textiles, especially with bleach-containing laundry products, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color.
Given the foregoing, there is clearly an ongoing need to identify materials which could be added to laundry detergent products that would associate themselves with the fibers of the fabrics and textiles laundered using such detergent products and thereby reduce or minimize the tendency of the laundered fabric/textiles to deteriorate in appearance. Any such detergent product additive material should, of course, be able to benefit fabric appearance and integrity without unduly interfering with the ability of the laundry detergent to perform its fabric cleaning function. Co-pending applications PCT/US98/19139 describes the use of hydrophobically modified cellulosic polymers which are found to provide excellent integrity benefits to fabrics.
The inventor has now found that when these hydrophobically modified cellulosic polymers are used in combination specific cationically charged compounds, namely having a quaternary ammonium group, such as specific quaternary ammonium surfactants, softeners and dispersants, the fabric care and fabric integrity can be further improved. Furthermore, the performance of the quaternary ammonium compound is improved, e.g. an surprisingly improved cleaning and/or softening and/or soil removal or whiteness or brightness maintenance is achieved when these materials are used together. It is also found that when the cellulosic material and the quatemary ammonium compound or compounds are present in an intimate mixture, such as in the form of an agglomerate, a compacted granule or a spray dried granule, these benefits are even more apparent.
It is believed that these benefits are achieved because the specific cellulosic material and the specific cationic compounds having a quatemary ammonium group, interact in such a manner that both materials enhance each others surface activity, resulting in a better interaction with or deposition onto the surface of the fabric. This then will result in improved performance of not only the cellulosic polymer, but also the quaternary ammonium compound, thus, an improved fabric integrity and improved cleaning, softening and/or soil removal or whiteness/brightness maintenance results. It is believed that when the cellulosic polymers and quaternary ammonium compound or compounds are present in an intimate mixture, e.g. in the same component or granule, this interaction between the materials is even more likely to occur or even stronger, resulting in even greater benefits
The present invention relates to a detergent composition or component, or additive comprising:
a) from 0.01% to 90% by weight, preferably form 0.05% to 50% by weight, of a salt of a quaternary ammonium compound; and
b) from 0.01% to 90% by weight, preferably from about 0.05% to about 20% by weight of a hydrophobically modified cellulosic polymer.
The compositions may be laundry detergents or additives, fabric softeners or fabric treatment products. The components can be contained in these compositions. The present invention also relates to the laundering or treating of fabrics and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent compositions or components described herein, or formed from the individual polymeric materials of such compositions or components. Laundering of fabrics and textiles in such washing solutions imparts fabric appearance benefits to the fabric and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness and also improved whiteness and/or brightness maintenance or even improved cleaning performance.
The cationic compounds and the cellulose material are preferably in an intimate mixture with one another. In one preferred embodiment, the compounds are intimately mixed prior to introduction to the composition or component of the invention.
Preferably, the mixture is present in an agglomerated, compacted or spray-dried particle, when the composition or component is solid.
Hereby it may be preferred that the compounds are mixed with an anionic surfactant, preferably LAS, as described herein after. It may also be preferred that a hydrotrope is admixed to this mixture, preferably STS. Also preferred in the mixture are inorganic and/or organic salts and acids and/or silicates or aluminosilicates, including zeolite, amorphous silicates, crystalline (layered) silicates, carbonate, bicarbonate, phosphate, citric acid, malic acid, maleic acid, tartaric acid or salts thereof, or mixtures of these ingredients.
The hydrophobically modified cellulosic polymers herein include polymers, oligomers, copolymers and also cross-linked polymers, oligomers and copolymers. The will herein be referred to as cellulosic based polymers. As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1,000 and polymers are molecules having an average molecular weight of greater than about 1,000. One suitable type of cellulosic based polymer herein has an average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1,000,000.
Depending on the application of the composition or component herein, the amount of cellulosic based polymers in the compositions or components may very. The cellulosic based polymers will generally be about 0.01% to about 90% by the weight of the detergent composition or component, more preferably from 0.05% to 20% or even from 0.05% to 15% by weight. In detergent compositions herein it may for example be preferred that the polymer is present at a level of from 0.05% to 10% by weight of the detergent composition, preferably from 0.05% to 5% or even from 0.05% to 3% or even 0.1% to 2% by weight. In detergent additives or components, the polymer may preferably be present at a level of 0.05% to 40% by weight of the component, or even from 0.05% to 20% or even 0.1% to 15% or even 1% to 10% by weight.
The cellulosic based polymers herein is preferably present in the composition or component in such an amount that the concentration of polymer in the wash is from 100 ppm to 10,000 ppm, preferably from 500 ppm to 7000 ppm or even from 1000 to about 3000 ppm.
The cellulosic based polymer for use herein is preferably of the following formula: 
wherein each R is selected from the group consisting of R2, RC, and 
wherein:
each R2 is independently selected from the group consisting of H and C1-C4 alkyl;
each RC is 
xe2x80x83wherein each Z is independently selected from the group consisting of M, R2, RC, and RH;
each RH is independently selected from the group consisting of C5-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2-hydroxyalkyl, (R4)3N-alkyl, (R4)3N-2-hydroxyalkyl, C6-C12 aryloxy-2-hydroxyalkyl, 
each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloalkylaminoalkyl and hydroxyalkyl;
each R5 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4)2N-alkyl, and (R4)3N-alkyl;
wherein:
M is a suitable cation selected from the group consisting of Na, K, 1/2Ca, and 1/2Mg;
each x is from 0 to about 5;
each y is from about 1 to about 5; and
provided that:
the Degree of Substitution for group RH is between about 0.001 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
the Degree of Substitution for group RC wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;
if any RH bears a positive charge, it is balanced by a suitable anion; and
two R4""s on the same nitrogen can together form a ring structure selected from the group consisting of piperidine and morpholine.
The xe2x80x9cDegree of Substitutionxe2x80x9d for group RH, which is sometimes abbreviated herein xe2x80x9cDSRHxe2x80x9d, means the number of moles of group RH components that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above.
The xe2x80x9cDegree of Substitutionxe2x80x9d for group RC, which is sometimes abbreviated herein xe2x80x9cDSRCxe2x80x9d, means the number of moles of group RC components, wherein Z is H or M, that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered ring as shown in the repeating unit of the general structure above. The requirement that Z be H or M is necessary to insure that there are a sufficient number of carboxy methyl groups such that the resulting polymer is soluble. It is understood that in addition to the required number of RC components wherein Z is H or M, there can be, and most preferably are, additional RC components wherein Z is a group other than H or M.
These polymers can for example be obtained by use of processes as described in co-pending application PCT/US98/19139 and PCT/US98/19142.
The compositions or components of the invention comprise a quaternary ammonium compound. This compound is preferably selected from quaternary ammonium surfactants, quaternary ammonium softeners, quaternary ammonium dispersants, described herein after. Highly preferred are the quatemary ammonium surfactants.
The levels of the quaternary ammonium surfactants used in detergent compositions of the invention are preferably from 0.1% to 20%, preferably from 0.4% to 7%, most preferably from 0.5% to about 5.0%, by weight of the detergent composition. The levels of the quaternary ammonium surfactants in components or additives of the invention are preferably from 0.1% to 90%, preferably from 0.5% to 50%, most preferably from 2% to about 30%, by weight of the detergent component or additive.
The levels of the quaternary ammonium softeners used in detergent compositions of the invention are preferably from 0.1% to 20%, preferably from 0.4% to 15%, most preferably from 0.5% to about 10%, by weight of the detergent composition. The levels of the quaternary ammonium surfactants in components or additive of the invention are preferably from 0.1% to 90%, preferably from 0.5% to 50%, most preferably from 2% to about 30%, by weight of the detergent component or additive.
The levels of the quaternary ammonium dispersant used in detergent compositions of the invention are preferably from 0.05% to 10%, preferably from 0.1% to 7%, most preferably from 0.5% to about 5.0%, by weight of the detergent composition. The levels of the quatemary ammonium surfactants in components or additive of the invention are preferably from 0.1% to 60%, preferably from 0.5% to 40%, most preferably from 0.5% to about 25%, by weight of the detergent component or additive.
Preferably, the cationic surfactant herein is selected from the group consisting of cationic mono-alkoxylated amine surfactants (not being the sodium salt of the cationic C12-C14 alkyl dimethyl ammonium ethanol surfactant), cationic bis-alkoxylated amine surfactants and mixtures thereof. Also preferred are salts of the cationic C12-C14 alkyl dimethyl ammonium ethanol surfactant.
The cationic surfactant herein can be a cationic mono-alkoxylated amine surfactant, which has the general formula I: 
wherein R1 is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl, most preferably both R2 and R3 are methyl groups; R4 is selected from hydrogen (preferred), methyl and ethyl; Xxe2x88x92 is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is a alkoxy group, especially a ethoxy, propoxy or butoxy group; and p is from 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.
Preferably the ApR4 group in formula I has p=1 and is a hydroxyalkyl group, having no greater than 6 carbon atoms whereby the xe2x80x94OH group is separated from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms. Particularly preferred ApR4 groups are xe2x80x94CH2CH2OH, xe2x80x94CH2CH2CH2OH, xe2x80x94CH2CH(CH3)OH and xe2x80x94CH(CH3)CH2OH, with xe2x80x94CH2CH2OH being particularly preferred. Preferred R1 groups are linear alkyl groups. Linear R1 groups having from 8 to 22 carbon atoms, or from 9 to 16 carbon atoms are preferred. Such a cationic surfactant which is highly preferred has a formula wherein R1 is a C8-C10 or a C12-C14 alkyl group, p is 1, A is ethoxy and R2 and R3 are methyl groups.
It has been found that mixtures of the cationic surfactants of formula I may be particularly effective, for example, surfactant mixtures in which R1 may be a combination of C8 and C10 linear alkyl groups, C9 and C11 alkyl groups, C12 and C14 alkyl groups.
Another highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula 
wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, especially C10-C14 alkyl, preferably C10 and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.
As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
When used in granular detergent compositions cationic mono-alkoxylated amine surfactants wherein the hydrocarbyl substituent R1 is C8-C14 can be preferred, because they enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.
The cationic surfactant herein can be a cationic bis-alkoxylated amine surfactant, which has the general formula II: 
wherein R1 is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, Xxe2x88x92 is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and Axe2x80x2 can vary independently and are at each selected from C1-C4 alkoxy, especially ethoxy, (i.e., xe2x80x94CH2CH2Oxe2x80x94), propoxy, butoxy and mixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
Highly preferred cationic bis-alkoxylated amine surfactants for use herein are of the formula 
wherein R1 is C10-C18 hydrocarbyl and mixtures thereof, preferably C10, C12, C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R1 is derived from (coconut) C12-C14 alkyl fraction fatty acids, R2 is methyl and ApR3 and Axe2x80x2qR4 are each monoethoxy.
Other cationic bis-alkoxylated amine surfactants useful herein include compounds of the formula: 
wherein R1 is C10-C18 hydrocarbyl, preferably C10-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R2 is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.
Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.
When used in granular detergent compositions in accord with the invention, cationic bis alkoxylated amine surfactants wherein the hydrocarbyl substituent R1 is C8-C14, can be preferred cationic surfactants, because they enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.
A cationic surfactant according to the present invention comprises at least one quatemized ammonium group and at least one primary, secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.